Zbornik radova Tehnološkog fakulteta u Leskovcu

ISSN 0352-6542 UDK 004/.007+3+5+6(05)

20 (2011), 52 – 60
UDK 66.011:628.473.3:628.4.08
Originalni naučni rad

KINETIC MODELS FOR DEGRADATION OF ORGANIC FRACTION

OF MUNICIPAL SOLID WASTE WITH DIFFERENT ADDITIVES*

Azra Helić, Ivan Petric, Edisa Avdihodžić Avdić

Faculty of Technology, University of Tuzla, Process Enginenering, Tuzla,
Bosnia and Herzegovina

The aim of this study is to propose kinetic models based on the change of organic
matter in the process of aerobic composting of municipal solid waste (MSW) with
different additives. Using nonlinear regression methods, kinetic parameters were
derived from experimental data. Based on various statistical parameters (correlation
coefficient (R2), adjusted correlation coefficient (R2adj), mean square standard deviation
(Rmsd), variance and 95% confidence interval), the results obtained were compared with
the results from the proposed kinetic models. Substrate temperature, O2 and CO2
concentrations (vol % d.b.) were continuously measured. Other analysis (moisture
content and total dry matter, organic matter and ash content, pH and electrical
conductivity) were carried out daily. Three new kinetic models were proposed, of
which model 3 gave the best results and the best value of statistical indicators, and it
d
 Mc 
has the following form: kT  O2(1a)  b(T 23)  pH c    , where: kT is the rate of
 T 
decomposition (g VS/g VS day-1), T is the process temperature (°C); Mc is a daily
moisture content in the material (% w.b.); O2 is a daily concentration of oxygen (%)
and a, b, c, d are constants. The comparison of numerical simulations results with
experimental data showed a very good agreement.

Key words: kinetic model, kinetic parameters, aerobic composting, MSW, nonlinear
regression.

*
Rad saopšten na IX Simpozijumu “Savremene tehnologije i privredni razvoj”, Leskovac,
21. i 22. oktobar 2011. godine
Adresa autora: Edisa Avdihodžić Avdić, Tehnološki fakultet, Univerzitet u Tuzli,
Univerzitetska 8, Tuzla, Bosna i Hercegovina
E-mail: edisa.avdihodzic@untz.ba

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INTRODUCTION

The composting process has a very important role in the management of MSW. One of
the main goals of the composting process for MSW is to maximize the rate of waste
degradation. The rate of waste degradation can be predicted by using the kinetic
models based on process parameters (substrate temperature, organic matter content,
moisture content, concentration of O2, pH, C/N ratio, particle size, etc.). Modeling the
composting kinetics plays an important role in designing and managing facilities for
composting, which are in strict accordance with market requirements and
environmental laws. A literature review showed that the most common form of the
kinetic model for the composting process has a reaction order of 1[1]. Most of existing
models are based on a few dynamic state variables as the moisture content and
substrate temperature. However, other dynamic state variables (O2 concentration, pH
and electrical conductivity) have also great influence on the composting process.
Moreover, most authors did not give important statistical parameters, or they did not
perform verification of their models to show agreements of numerical simulations
results with experimental data. The aim of this study is to propose new kinetic models
based on the experimental data obtained in laboratory conditions using nonlinear
regression. The experimental data will be also applied to three existing literature
kinetic models in order to show the differences between new and existing kinetic
models.

EXPERIMENTAL PART

Materials and methods

Separated MSW, poultry manure, mature compost and sawdust, were used in the
experiment. Basic physical and chemical characteristics are shown in Table 1.

Table 1. Basic physico-chemical characteristics of separated MSW, poultry manure, compost

and sawdust, before mixing (three measurements, mean value)
Material Total Moisture Organic ASH pH El.cond. C N
solids (%w.b.) matter (%d.b.) (dS m-1) (%) (%)
(%w.b.) (%d.b.)
MSW 40.17 59.83 91.69 8.31 4.98 1.19 50.94 0.66
Poultry 28.97 71.03 78.89 21.11 8.31 3.77 43.83 5.02
manure
Sawdust 89.97 10.03 99.9 0.1 5.31 0.24 55.50 0.28
Compost 67.49 32.51 40.31 59.69 6.92 0.35 22.39 1.21
w.b. – wet basis, d.b. – dry basis

The collected waste was prepared in the laboratory (by chopping and mixing). Part of
the prepared waste was separated for analysis while the remaining waste was mixed
with the rest of the material for composting. After mixing with other materials, filling
of the reactors was performed. During the process, the substrate temperature (every 15

53
minutes) and the temperature of the surrounding air were measured continuously. The
concentrations of O2 and CO2 (in vol% s.b.), moisture and total solids [2], organic
matters and ash[2], pH and electrical conductivity[2] were daily measured. Table 2
shows the basic physico-chemical properties of the mixture of MSW, poultry manure,
sawdust and compost in both reactors. More details about the experiment can be found
in the reference[3].
Table 3 shows percentage compositions for mixtures of MSW, poultry manure,
sawdust and mature compost in both reactors.

Table 2. Characterization of a mixture of municipal solid waste, poultry manure,

sawdust and compost in the reactors (three measurements, mean value)

Reactor Moisture Total Organic Ash pH El.cond. C N

(%w.b.) solids matter (%d.b.) (dSm-1) (%) (%)
(%w.b.) (%d.b.)
1 45.56 54.44 87.53 12.47 5.17 1.50 48.63 1.21
2 60.38 39.62 83.89 16.11 6.37 2.62 46.61 1.38
w.b. – wet basis, d.b. – dry basis

Table 3. Percentage compositions of composting mixtures in the reactors

Reactor MSW Poultry manure Sawdust Compost

(%) (%) (%) (%)
1 60 20 10 10
2 42.86 42.86 7.14 7.14

Figure 1 shows a specially designed laboratory reactor used in the experiment.

Figure 1. Reactor for aerobic composting of MSW

Numerical simulation of kinetic models

In order to determine a decomposition rate of waste and kinetic parameters, the
experimental data were applied to three existing literature kinetic models ([4], [5], [6]),
54
and three new models (Table 4). The determination of kinetic parameters with
nonlinear regression was carried out based on the experimental data obtained from the
process in specially designed laboratory reactors (O2 and CO2 concentrations, moisture
content, pH, electrical conductivity and substrate temperature). Based on four
statistical indicators (factor correlations, adjusted factor correlations, mean squared
standard deviation and variance), experimental results will be compared with the
results from proposed kinetic models in order to conclude which proposed models
gives the best results (that is most appropriate for the description of the data obtained
by experiment). For the determination of kinetic parameters, numerical software
package Polymath[7] and Levenberg-Marquardt method [8] were used.

Table 4. Applied kinetic models

No. model Kinetic model Literature

1 (T  23) [4]
kT  k23  a
  M  c   T  f  
k T  a  expb   i      [5]
2   d   g  
  M  
3 k T  a  exp (b  T )   c  c   [6]
  T  
  M  This study
1 k T  a  b O2  exp (c  T )   d  c 
  T 
  O   EC  This study
2 k T  a  exp (b  T )   c  2    d  
  T   T 
d
(1a ) M  This study
3 k T  O2  b (T 23)  pH c   c 
 T 
Legend: k23 - reaction rate constant of degradation at 23°C (OT g / g day OT);kT - reaction rate constant of
degradation (OT g / g day OT); T - temperature of the process (°C); MC-daily moisture content in the
material (% mb); a, b, c, d, f, g - constants; pH-pH value; EC-electrical conductivity (dS m-1), O2 - oxygen
concentration (%).

RESULTS AND DISCUSSION

Experimental data which were used to determine kinetic parameters of proposed

models can be found in the reference[2]. Tables 5, 6, 7 and 8 show the values of kinetic
parameters for three existing literature models and three new models that were
proposed in this study, with the values of the statistical analysis. In accordance with the
results of the statistical analysis, the proposed model 3 was the best for the description
of the data obtained by experiment:
d
M 
kT  O2(1 a )  b(T  23)  pH c   c 
 T 

55
Unlike other models, the above model has no exponential form. This model is
characterized by the best values of all the statistical indicators. Successful convergence
of nonlinear regression models is often dependent on the use of good initial
assumptions. Good initial parameter assumptions can usually be obtained by
transforming the nonlinear into linear form and can be used for a linear regression or a
multiple linear regression. The initial estimates are required for all model parameters.
Models 1 and 2 are first dealt with the multiple linear regression and nonlinear
regression. Because of the complexity, model 3 can be solved only by using the
nonlinear regression, taking the used values from the literature[6] as the initial default
values. One of the reasons for the appearance of disagreement among the results lies in
the heterogeneity of the material for composting, which implies that it is difficult to
obtain ideal experimental results for a statistical analysis. The main assumption was
that the decomposition of organic matter is a function of time describing the kinetic
model of first order, because the review of the literature showed that this is the most
common form for the description of the organic matter degradation. However, further
research could be done in a way that is not based on this assumption, but to
simultaneously determine the reaction order and kinetic parameters. In this way, it is
possible to avoid the before mentioned disagreement among the results. Also, we
should bear in mind the problem of heterogeneity of MSW. Figures 2 and 3 show the
results of the comparison of experimental data and model 3 for the content of organic
matter (%) in the reactors 1 and 2. A very good agreement between the experiment and
the model was obtained.

Figure 2 Verification of the model for the Figure 3 Verification of the model for the
content of organic matter (R1) content of organic matter (R2)

The calculated values of maximum and mean difference between the experiment and
the model for the content of organic matter were 3.91%, and 0.14% (for R1), and
3.93% and 0.49% (for R2), which indicates that the proposed model describes the
decomposition process of MSW well. In determining the kinetics of MSW in a
mechanical-biological treatment plant[1], the obtained experimental data were used to
describe the process of composting with the first order kinetic model, which is based
on changing the concentration of volatile solids. The obtained values of the reaction
rate constants were within the interval from 0.043 to 0.082 days-1, while calculated
values in this work were 0.0632 day-1 (for R1), and 0.0635 day-1 (for R2). These values

56
are also close to the values obtained by other researchers ([9], [10], [11]), which is another
indicator for the success of the experiment in laboratory conditions.

CONCLUSIONS

The determination of kinetic parameters with a nonlinear regression was carried out
based on experimental data which were obtained from the process in specially designed
laboratory reactors. The experimental data were applied to three existing literature
kinetic models. The results of a statistical analysis used to estimate the kinetic
parameters of the model showed that better results can be achieved by proposing new
kinetic models. Three new kinetic models were proposed, of which model 3 gave the
best results and the best value of statistical indicators and it has the following form:
d
M 
kT  O2(1 a )  b(T  23)  pH c   c 
 T 
Unlike other models, model 3 has no exponential form. Its specificity is reflected in the
fact that it is based on experimental data of: pH, electrical conductivity and
concentration of O2, which were not covered by either of the existing literature models.
The maximum difference between the experiment and model 3 for the amount of
organic matter was 3.91% for the first reactor and 3.93% for the second reactor, a mean
difference 0.14% for first reactor and 0.49% for the second reactor. The mean values of
reaction rate constants of degradation of MSW were to 0.0632 day-1 for the first reactor
and 0.0635 day-1 for the second reactor. These values of reaction rate constants showed
a very good agreement with the values of other researchers.

57
 Table 5. The results of a statistical analysis and kinetic values Table 6. The results of a statistical analysis and values of kinetic
parameters for the existing models in literature (R1) parameters for the existing models in literature (R2)
Model Kinetic 95 % R2 R2adj Rmsd Variance Model Kinetic 95 % R2 R2adj Rmsd Variance
parameters confid. parameters confid.
a=0.0042 0.00026 0.9962 0.996 0.0029 0.00022 a=0.3280 0.00060 0.8455 0.838 0.0197 0.00979
1 k =0.3444 0.00465 1 k23=2.1513 0.00454 0.019
23
a=1.85∙10-5 0.00118 0.9974 0.997 0.0024 0.00015 a=1.6∙10-7 1.7∙10-9 0.6093 0.570 0.0313 0.02602
2 b=-0.2117 1.36070 2 b=-0.1070 0.00044 0.031
c=5.2776 11.0444 c=5.0399 0.00464
3 a=0.0283 0.02071 0.9973 0.996 0.0024 0.00019 3 a=0.000727 5.81∙10-5 0.9968 0.995 0.0028 0.00024
b=-14.843 1.99420 b=-9.07991 0.09797 0.002
c=39.5454 0.84563 c=19.83829 0.03488
d=17.5231 0.51815 d=4.091303 0.00321
f=54.5526 0.79133 f=48.05039 0.01141
g=16.7311 0.43229 g=2.263091 0.00157

Table 7. The results of a statistical analysis and kinetic values Table 8. The results of a statistical analysis and values of kinetic
parameters for the proposed kinetic model (R1) parameters for the proposed kinetic model (R2)
Model Kinetic 95 % con. R2 R2adj Rmsd Variance Model Kinetic 95 % con. R2 R2adj Rmsd Variance
parameters parameters
a=0.0383 1.11∙10-7 0.9996 0.999 9.4∙10-4 2.51∙10-5 a=2.6518 9.73∙10-5 0.9993 0.999 0.0012 4.38∙10-5
1 b=0.8206 2.53∙10-6 1 b=0.7886 3.83∙10-5
c=-0.0032 1.27∙10-7 c=-0.0384 1.53∙10-6
d=1.1536 9.65∙10-7 d=0.0448 1.44∙10-5
a=3.0338 8.93∙10-5 0.9995 0.999 9.6∙10-4 2.59∙10-5 a=0.1811 5.57∙10-7 0.9995 0.999 0.0010 3.08∙10-5
b=-0.0949 1.29∙10-6 b=-0.0253 1.28∙10-7
2 2
c=-5.4244 0.00097 c=-5.5839 1.32∙10-4
d=-17.994 0.00044 d=-22.505 2.79∙10-5
a=1.4802 0.00581 0.9998 0.999 5.4∙10-4 8.34∙10-6 a=1.5046 2.22∙10-7 0.9998 0.999 0.0005 7.65∙10-6
3 b=0.9138 0.00765 3 b=0.96894 7.91∙10-7
c=0.02123 0.02515 c=-0.5889 8.28∙10-7
d=-2.9434 0.03899 d=-2.3559 1.64∙10-6
Legend: R2 - correlation coefficient R2adj - adjusted correlation coefficient, Rmsd-mean square standard deviation
58
Literature

[1] M. Baptista, F. Antunes, M. Souteiro Gonçalves, B. Morvan and A., Silveira,

Waste Manage. 30 (2010) 1908
[2] APHA (American Public Health Association), Standard Methods for the
Examination of Water and Wastewater, Washington DC (1995)
[3] Avdihodžić Avdić, E, Laboratorijska i numerička simulacija procesa kompostiranja
komunalnog krutog otpada sa prisilnom aeracijom u reaktoru. Magistarski rad,
Tehnološki fakultet Univerziteta u Tuzli, 2011
[4] R. T. Haug, The practical Handbook of Compost Engineering. Lewis Publishers,
Boca Ratan, FL, 1993, p. 718
[5] K. Ekinci, H. M. Keener, F. C. Michael and D.L. Elwell, Effects of temperature and
initial moisture content on the composting rate of short paper fiber and broiler litter,
ASAE Annual Meeting, California, (2001)
[6] R. Külcu and O. Yaldiz, Bioresour. Technol. 93 (2004) 49
[7] POLYMATH, Educational Version 6.0, Michael Elly, The CACHE Corporation
USA, (2004)
[8] W. H. Press, P. B. Flannery, S. A. Teukolsky and W.T. Vetterling, Numerical
Recipes, 2nd Ed., Cambridge University Press, Cambridge, (1992)
[9] I. Tosun, M. T. Gönüllü, E. Arslankaya and A. Günay, Bioresour. Technol. 99
(2008) 6143
[10] M. F. Hamoda, H. A. A. Qdais and J. Newham, Resour. Conser. Recycl. 23 (1998)
209
[11] Q. H. Bari and A. Koenig, Waste Manage. Res. 18 (2000) 313

IZVOD

KINETIČKI MODELI ZA RAZGRADNJU ORGANSKE FRAKCIJE

KOMUNALNOG KRUTOG OTPADA SA RAZLIČITIM DODACIMA
(Originalan naučni rad)
Azra Helić, Ivan Petric i Edisa Avdihodžić
Tehnološki fakultet Univerziteta u Tuzli, Procesno inženjerstvo, Tuzla, Bosna i Hercegovina

Cilj rada je bio da se predlože kinetički modeli koji su zasnovani na promjeni sadržaja
organskih tvari za proces aerobnog kompostiranja komunalnog krutog otpada sa
različitim dodacima. Primjenom metoda nelinearne regresije, određeni su kinetički
parametri na osnovu eksperimentalnih podataka. Na osnovu različitih statističkih
pokazatelja (faktor korelacije (R2), podešeni faktor korelacije (R2adj), srednja kvadratna
standardna devijacija (Rmsd), varijansa i 95% interval pouzdanosti), dobijeni rezultati su
upoređeni sa rezultatima iz predloženih kinetičkih modela. Kontinuirano su mjerene
temperatura supstrata, koncentracije O2 i CO2 (u vol % s.b.). Svakodnevno su vršene i
ostale analize (sadržaj vlage i ukupnih suhih tvari, sadržaj organskih tvari i pepela, pH-
vrijednost i električna vodljivost). Predložena su tri nova kinetička modela, od kojih
59
model 3 daje najbolje rezultate i najbolje vrijednosti statističkih pokazatelja i ima
d
 Mc 
sljedeći oblik: kT  O2(1a )  b (T 23)  pH c    gdje su: kT konstanta brzine reakcije
 T 
(g OT/g OT dan-1); T je temperatura procesa (°C); Mc dnevni sadržaj vlage u materijalu
(% m.b.); O2 dnevna koncentracija kisika (u vol % s.b.) i a, b, c, d su konstante.
Poređenje rezultata numeričkih simulacija sa eksperimentalnim podacima pokazalo je
jako dobro slaganje.

Ključne riječi: kinetički model, kinetički parametri, aerobno kompostiranje, komunalni

kruti otpad, nelinearna regresija.

Primljen / Received: 13. maj 2011. godine

Prihvaćen / Accepted: 06. jun 2011. godine

60